WO2024083601A1 - Couche de diffusion gazeuse ayant une faible déformabilité plastique et une qualité de surface élevée et son procédé de fabrication - Google Patents

Couche de diffusion gazeuse ayant une faible déformabilité plastique et une qualité de surface élevée et son procédé de fabrication Download PDF

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Publication number
WO2024083601A1
WO2024083601A1 PCT/EP2023/078170 EP2023078170W WO2024083601A1 WO 2024083601 A1 WO2024083601 A1 WO 2024083601A1 EP 2023078170 W EP2023078170 W EP 2023078170W WO 2024083601 A1 WO2024083601 A1 WO 2024083601A1
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WIPO (PCT)
Prior art keywords
gas diffusion
diffusion layer
mpa
gdl
treatment
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Ceased
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PCT/EP2023/078170
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German (de)
English (en)
Inventor
Achim Bock
Kristof Klein
Christoph Dr. RAKOUSKY
Hannes Dr. BARSCH
Matthias Dr. LÖBLE
Amélie VON SPEE
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Carl Freudenberg KG
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Carl Freudenberg KG
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Priority to KR1020257012291A priority Critical patent/KR20250069639A/ko
Priority to JP2025521533A priority patent/JP2025536291A/ja
Priority to CN202380070728.9A priority patent/CN119998967A/zh
Priority to EP23789601.4A priority patent/EP4605990A1/fr
Publication of WO2024083601A1 publication Critical patent/WO2024083601A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8803—Supports for the deposition of the catalytic active composition
    • H01M4/8807—Gas diffusion layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
    • H01M4/8882—Heat treatment, e.g. drying, baking
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
    • H01M4/8896—Pressing, rolling, calendering
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/023—Porous and characterised by the material
    • H01M8/0234—Carbonaceous material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M2008/1095—Fuel cells with polymeric electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to a method for producing a gas diffusion layer for a fuel cell with low plastic deformability (low setting behavior) and a good surface quality.
  • the invention further relates to the gas diffusion layers obtainable by this method and to a fuel cell containing such a gas diffusion layer.
  • Fuel cells use the chemical conversion of a fuel, particularly hydrogen, with oxygen to form water to generate electrical energy.
  • hydrogen-oxygen fuel cells hydrogen or a hydrogen-containing gas mixture is fed to the anode, where electrochemical oxidation takes place with the release of electrons (H 2 -> 2 H + + 2 e-).
  • the protons are transported from the anode chamber to the cathode chamber via a membrane which separates the reaction chambers from one another in a gas-tight manner and electrically insulates them.
  • the electrons provided at the anode are fed to the cathode via an external conductor circuit.
  • Oxygen or an oxygen-containing gas mixture is fed to the cathode, whereby the oxygen is reduced and the electrons are absorbed.
  • the oxygen anions formed react with the protons transported across the membrane to form water (1/2 O 2 + 2 H + + 2 e- -> H 2 O).
  • PEMFC low-temperature proton exchange membrane fuel cells
  • PEM polymer electrolyte membrane fuel cells
  • a catalyst layer is applied to the anode and cathode sides of the gas-tight, electrically insulating, proton-conducting membrane, which forms the electrodes and usually contains platinum as a catalytically active material. active metal. The actual redox reactions and charge separations take place in the catalyst layers.
  • the membrane and catalyst layers form a unit, which is also known as a CCM (catalyst coated membrane).
  • CCM catalyst coated membrane
  • GDL gas diffusion layer
  • the membrane, electrodes and gas diffusion layer form the membrane electrode unit (MEA).
  • Flow distribution plates are arranged between the membrane electrode units, which have channels for supplying the adjacent cathode and anode with process gases and usually also have internal cooling channels.
  • Gas diffusion layers for fuel cells typically consist of a carbon fiber substrate that is made hydrophobic with fluoropolymers (e.g. PTFE) and then coated with a microporous layer (MPL).
  • MPL usually consists of a fluorine-containing polymer as a binder (e.g. PTFE) and an electrically conductive material, with carbon materials such as carbon black or graphite powder often being used.
  • the gas diffusion layers are of key importance for the function and performance of the fuel cell. On the one hand, they transport the process components consumed and generated in the electrode reactions and, on the other hand, they conduct the electrons formed and consumed in the half-cell reactions and the heat generated during the reaction to the flow distribution plates.
  • the GDL also acts as a mechanical balance between the macrostructured flow distribution plate and the catalyst layers. For this, component tolerances must be compensated and the compression pressure distributed.
  • the GDL also serves as mechanical protection for the very thin membranes that are exposed to high loads in the fuel cells. The sensitive membranes should not be damaged by the gas diffusion layer and its components. Therefore, high demands are placed on the mechanical properties and surface properties of the GDL.
  • a major problem with fiber-based gas diffusion layers is the potential damage to the fuel cell membrane caused by an inhomogeneous surface of the gas diffusion layer or protruding fibers. These fibers are usually very stiff and brittle. In addition, the fiber thickness is often in the range of the thickness of the fuel cell membrane, so there is a risk that the membrane will be penetrated by fibers and a short circuit will be caused. In the worst case, a short circuit caused by fiber penetration of the membrane can lead to the failure of the entire fuel cell stack. Other sources of error that can lead to similar failures or to a significant reduction in the service life of the stack include, for example, a very rough MPL surface or impurities of varying hardness integrated into the MPL. Since the membrane can be exposed to considerable mechanical stress during operation of the fuel cell, the stack failure can also occur at a later point in time.
  • the membrane of a fuel cell is very thin, usually just a few pm thick. Typical thicknesses are in the range of 8 to 50 pm, although membranes with thicknesses of 5 pm are already being tested in some cases. It is to be expected that with the increasing use of fuel cells in automotive applications, there will be a need for the thickness of all flat components (membranes, GDL/MPL, others) to continue to decrease. A very large performance problem is caused by internal short circuits, which can be caused by protruding fibers of the GDLs resting on the membrane. There is therefore a need to avoid protruding fibers and/or to smooth the MPL surfaces of the GDL.
  • GDLs When used in fuel cells, GDLs are usually heavily compressed.
  • the properties of GDLs as a result of compression can be characterized by the proportion of elastic and plastic deformation.
  • plastic deformation the gas diffusion layer does not return 100% to its original shape after a load, but remains permanently deformed.
  • the property of a material to permanently change its shape when a stress is applied, i.e. its deformability, is also referred to as "settling". Materials that have low plastic deformability have low settling behavior.
  • the settling behavior of the GDLs known from the state of the art still needs improvement. If the GDL is clamped in the fuel cell stack under high pressures, it will set due to the clamping forces and dynamic force changes during operation.
  • WO 2022/002932 A1 describes a gas diffusion layer for a fuel cell, wherein at least one physical property, selected from hydrophobicity and permeability, changes in at least one direction along the largest areal extent. Specifically, it is described, for example, to control the hydrophobicity via the content of a hydrophobicizing material (such as PTFE) and the permeability via the porosity of the gas diffusion layer.
  • a microporous layer When a microporous layer is applied, its thickness can be influenced, which, among other things, leads to a changing local penetration depth into the carrier layer.
  • the disclosure of this application is not very specific and there is a lack of information on the implementation of the concepts described, as well as a reproducible embodiment and application data.
  • EP 3957789 A1 describes a gas diffusion layer which, despite its low density, has a high thermal conductivity and has good handleability and cell performance.
  • the GDL comprises a carbon fiber felt containing carbon fibers with an average fiber diameter of 5 to 20 pm, wherein at least a portion of the carbon fibers forming the carbon fiber felt has a flat portion in which, in a planar view of the surface of the carbon fiber felt, a maximum value of the fiber diameter is observed which is 10 to 50% larger than the average fiber diameter, and the frequency of the flat portions on the surface of the carbon fiber felt is 50 to 200/mm 2 .
  • WO 2020/165075 A1 describes a method for producing a gas diffusion layer, which comprises the following steps: a) preparing a carrier-binder paste containing a solvent, a fluorinated binder and conductive carrier particles, b) preparing an adhesive composition comprising a solvent, a fluorinated binder and essentially no or equal to or less than 15% by weight of conductive carrier particles, based on the total weight of the fluorinated binder and all conductive carrier particles; and c) combining a layer of the carrier material, a layer of the adhesive composition and a layer of the carrier-binder paste, wherein the layer of the adhesive composition is applied between the layer of the carrier material and the layer of the carrier-binder paste, and pressing the combination of carrier material, adhesive composition and carrier-binder paste at a pressure of at least 15 kilopascals (0.15 bar) and/or heating the combination of carrier material, adhesive composition and carrier-binder paste to a temperature of at least 300°C.
  • the aim of this document is to provide mechanically stable gas diffusion electrodes in which the carrier-binder layer, which is preferably designed as a microporous layer, is firmly connected to the carrier material.
  • the additional adhesive layer which is free of electrically conductive particles or contains only a small amount of them.
  • the layers are pressed together at a maximum pressure of 2.5 MPa and a temperature of at least 300°C, with long treatment times of at least 15 minutes and preferably 1 to 4 hours.
  • the additional binder layer between the substrate and the MPL increases the number of process steps required, and the long pressing time makes industrial applicability very difficult.
  • JP 2007242378 A describes a gas diffusion layer consisting of porous sintered carbon particles and water-repellent particles.
  • carbon particles and water-repellent particles are dispersed in water in the presence of a non-ionic surfactant, concentrated under phase inversion and sintered.
  • This sintered film is peeled off, pulverized again and the resulting sintered coarse particles are hot-pressed in a mold to form a GDL.
  • a fiber-based substrate in the final GDL can be dispensed with, so that it only consists of coarse carbon-based particles and water-repellent particles.
  • Such a procedure is likely to lead to disadvantages in further processing during cutting and production of the cell stacks as well as in the stability of the cell.
  • EP 3276718 A1 describes a porous carbon electrode substrate that hardly causes short circuits when used in a fuel cell. Carbon fibers that protrude from the substrate surface or are caused to protrude when the carbon electrode substrate is subjected to pressure is set, and short carbon fibers that are insufficiently bonded to the substrate surface are sufficiently removed. For production, short carbon fibers and a binder resin are used that contains a carbon content of at least 35 wt.% and that carbonizes when heated. The resulting GDL substrate is therefore based on a completely resin-impregnated fiber material.
  • EP 3396753 A1 describes a gas diffusion electrode that is less susceptible to the occurrence of a short-circuit current when used in a fuel cell.
  • the GDL substrate comprises short carbon fibers that are bound with a carbon resin, the gas diffusion electrode having a multilayer structure with preferably at least two microporous layers that differ in their layer filling rate, and the microporous layer(s) must have sufficient thicknesses under pressure load.
  • a large number of measures are described, e.g. pressure treatment of the precursor substrate before carbonization of the binder resin and increasing the temperature in the carbonization step. Only in the event that further reduction is desired, post-treatment by calendering, followed by blowing with air and suction, is described.
  • US 2019/0344405 describes an adhesive device for bonding a gas diffusion layer within a fuel cell.
  • This device has a suction device and is intended to bind or remove fluffy or loose fibers from a gas diffusion layer.
  • the use of an additional device increases the manufacturing costs.
  • it is questionable whether the use of this device solves the problem of internal short circuits that can be caused by protruding fibers of the GDLs resting on the membrane.
  • the invention is based on the object of avoiding or at least reducing the disadvantages described above.
  • gas diffusion layers with a good property profile and especially with very good surface properties and with significantly improved setting behavior can be achieved, if the gas diffusion layer is subjected to post-treatment at increased pressure and temperature.
  • Hot-compressed gas diffusion layers are characterized in particular by a considerably smoother surface on the side(s) coated with a microporous layer. This results in a considerably lower probability of short circuits caused by protruding fibers and impurities on the surface of the MPL, by other causes of a rough surface or other effects that occur during operation of the fuel cell and can lead to penetration of the membrane.
  • the plastic deformation component of the GDL can be significantly reduced by post-treatment at increased pressure and temperature.
  • the transport properties of the GDL can also be controlled by post-treatment. Properties such as gas permeability and dry diffusion length can thus be controlled independently of the material composition of the gas diffusion layer.
  • a first subject of the invention is a method for producing a gas diffusion layer for a fuel cell, comprising
  • a microporous layer on at least one of the surfaces of the fiber material comprising conductive particles in a matrix of a polymeric binder, in which i) a flat electrically conductive fiber material A) is provided, ii) the fiber material provided in step i) is coated with a precursor to form a microporous layer, iii) the coated fiber material obtained in step ii) is subjected to a post-treatment at increased pressure and optionally increased temperature.
  • the process according to the invention results in a gas diffusion layer with a reduced plastic deformability compared to a non-post-treated gas diffusion layer.
  • a gas diffusion layer with a reduced compression set value is achieved compared to a non-treated gas diffusion layer.
  • the process according to the invention especially the post-treatment in step iii), achieves a gas diffusion layer with a smoother surface of the at least one microporous layer.
  • step iii) is carried out at an elevated pressure of at least 0.5 MPa and an elevated temperature of at least 100°C.
  • a special embodiment is a method for achieving a gas diffusion layer with one, preferably two, particularly preferably three, in particular four of the following properties: a compression set value at 1.0 MPa of at most 5 pm, determined on a GDL with a basis weight of 95 to 100 g/m 2 and an MPL loading of 15 to 22 g/m 2 on an annular sample with an inner diameter of 45 mm and an outer diameter of 56 mm, wherein the sample is subjected to three load cycles from 0.025 MPa to 1.0 MPa and the compression set value results from the difference between the thickness measured at 1.0 MPa in the first load cycle and in the third load cycle, a reduction in the mean roughness value R a , determined according to DIN EN ISO 4288:1998-04 using the stylus method, compared to a non-treated gas diffusion layer of at least 10%, a reduction in the roughness depth R z , determined according to DIN EN ISO 4288:1998-04 using the stylus method, compared to a non-treated gas diffusion layer of at least 10%
  • Another object of the invention is a gas diffusion layer obtainable by a process as described above and below.
  • Another object of the invention is a gas diffusion layer for a fuel cell, comprising
  • Another object of the invention is a fuel cell which comprises at least one gas diffusion layer as defined above and below.
  • Another object of the invention is the use of a gas diffusion layer as defined above and below, or obtainable by a process as defined above and below, in a proton exchange membrane fuel cell.
  • gas diffusion layers have very good surface properties.
  • Gas diffusion layers treated at elevated pressure and preferably elevated temperature are characterized in particular by significantly smoother surface on the side(s) coated with a microporous layer.
  • the gas diffusion layers have a significantly lower probability of short circuits due to penetration of the proton exchange membrane, which can occur especially due to protruding fibers, contaminants on the surface of the MPL or other causes of a rough surface.
  • the gas diffusion layers have significantly improved setting behavior.
  • the plastic deformation component of the GDL can be significantly reduced by the post-treatment according to the invention at increased pressure and preferably increased temperature.
  • the transport properties of the gas diffusion layer can also be specifically influenced by the post-treatment according to the invention. This means that properties such as gas permeability and dry diffusion length can be controlled independently of the material composition of the gas diffusion layer.
  • the gas diffusion layers according to the invention can be produced easily and inexpensively.
  • the method according to the invention comprises the following steps: i) providing a flat, electrically conductive fiber material A), ii) coating the fiber material provided in step i) with a precursor to form a microporous layer B), wherein the composition of the precursor is varied to produce a gradient, iii) post-treating the coated fiber material obtained in step ii) at increased pressure and optionally increased temperature.
  • the treatment in step iii) is carried out at an increased pressure of at least 0.5 MPa and an increased temperature of at least
  • the treatment in step iii) is carried out at a pressure in the range from 0.5 to 10.0 MPa (5 to 100 bar), particularly preferably from 1.5 to 8.0 MPa.
  • the treatment in step iii) is carried out at a temperature in the range from 100 to 350°C, particularly preferably from 120 to 330°C, in particular from 150 to 320°C.
  • the treatment in step iii) is carried out in a press for a period of 5 seconds to 5 minutes, preferably 10 seconds to 2 minutes.
  • the treatment in step iii) is carried out in a calender over a period of time from greater than 0 seconds to 10 seconds, preferably from 0.1 seconds to 5 seconds.
  • step iii For the post-treatment in step iii), conventional devices such as single or multi-stage presses, endless belt presses or calenders can be used. In a special embodiment, at least one double belt press is used for the post-treatment in step iii). In another special embodiment, at least one calender is used for the post-treatment in step iii).
  • Double-belt presses are suitable for the treatment of both endless web-shaped materials and section-shaped materials (sheet material).
  • Double-belt presses have two endlessly rotating press belts between which the GDL web is post-treated under the influence of pressure and, if necessary, heat while being transported in the forward direction. The belts are aligned parallel to one another and there is a gap between the upper and lower belts that can be opened and closed to adapt to the thickness of the GDL material and to set the desired properties.
  • the treatment in step iii) is carried out in a double belt press.
  • the treatment in step iii) is carried out in a double belt press at a pressure in the range of 1 to 8 MPa (10 to 80 bar) and at a temperature in the range of 200 to 350°C.
  • the calender used in the process according to the invention is Calender a 2-roll calender.
  • the gas diffusion layer can be passed through the calender once or repeatedly, e.g. 1, 2, 3, 4, 5 or more than 5 times.
  • the calender rolls can be arranged in a geometry suitable for calendering the gas diffusion layers.
  • a two-roll calender can have a vertical, inclined or horizontal arrangement of the rolls.
  • a three-roll calender can have a vertical arrangement, a staggered upper roll or staggered lower roll.
  • a four-roll calender can have an L arrangement, an inverted L arrangement, an S arrangement, a Z arrangement or another arrangement of the rolls.
  • the treatment in step iii) is carried out in a calender at a line pressure in the range of 5 to 500 N/mm, preferably 10 to 100 N/mm.
  • the calendering in step iii) is carried out at a speed of 0.05 m/min to 30 m/min.
  • the treatment in step iii) takes place in a calender.
  • the treatment in step iii) takes place in a calender at a roll temperature in the range from 130 to 220°C at a line pressure in the range from 8 to 80 N/mm and a web speed of 1 to 10 m/min.
  • a nonwoven generally refers to a fabric that consists mainly of individual fibers, the cohesion of which is essentially only provided by their own adhesion.
  • the conversion of a nonwoven into a nonwoven material by creating a stronger bond between the fibers than is present in the nonwoven is carried out by nonwoven bonding processes, which are usually divided into mechanical, chemical and thermal processes.
  • Nonwovens, nonwoven fabrics and processes for their production are described in H. Fuchs, W. Albrecht, Vliesstoffe, 2nd edition, Wiley-VCH, Weinheim, Germany.
  • the flat, electrically conductive material A) and the gas diffusion layer used according to the invention are a flat structure that has an essentially two-dimensional, flat extension and a smaller thickness.
  • the gas diffusion layer according to the invention has a base area that generally corresponds essentially to the base area of the adjacent membrane with the catalyst layers and the base area of the adjacent flow distributor plate.
  • the shape of the base area of the gas diffusion layer can be, for example, polygonal (n-sided with n>3, e.g. B. triangular, square, pentagonal, hexagonal, etc.), circular, circular segment-shaped (e.g. semicircular), elliptical or elliptical segment-shaped.
  • the base area is preferably rectangular or circular.
  • An orthogonal coordinate system can be used to describe the GDL, whereby the base area of the GDL lies in the plane spanned by the x-axis and the y-axis (also referred to as the x,y plane).
  • the orthogonal z-axis is used to describe the material thickness.
  • the x-axis is also described as the roll direction (machine direction, MD) and the y-axis as the counter-roll direction (cross machine direction, CMD).
  • MD machine direction
  • CMD cross machine direction
  • the gas diffusion layer comprises as component A) at least one electrically conductive flat fiber material.
  • component A) comprises a fiber material selected from nonwovens, papers, fabrics and combinations thereof.
  • Suitable substrate materials are fiber materials that are themselves conductive or are made conductive by adding conductive additives such as carbon or metal particles.
  • suitable substrate materials are carbon fibers, glass fibers, fibers of organic polymers such as polypropylene, polyester, polyphenylene sulfide, polyether ketones and mixtures thereof.
  • the fibers contained in the fiber material A) preferably comprise or consist of carbon fibers (carbon fibers, carbon fibers). Such fiber materials particularly advantageously meet the requirements of the GDL for gas diffusivity, liquid water permeability, electrical and thermal conductivity.
  • the fiber material A) is preferably selected from carbon fiber fabrics, carbon fiber papers and carbon fiber nonwovens.
  • the fiber material A) comprises at least one carbon fiber nonwoven fabric or the fiber material A) consists of a carbon fiber nonwoven fabric.
  • the carbon fibers can be produced in the usual way, with polyacrylonitrile fibers (PAN fibers) preferably being used as the starting material.
  • PAN fibers are produced by radical polymerization of a monomer composition which preferably contains at least 90% by weight of acrylonitrile, based on the total weight of the monomers used for polymerization.
  • the polymer solution obtained is spun into filaments, e.g. by wet spinning and coagulation, and gathered into ropes.
  • oxidative cyclization also referred to as oxidation for short
  • oxygen-containing atmosphere at elevated temperatures of about 180 to 300 °C.
  • the resulting chemical The dimensional stability of the fibers is improved by cross-linking.
  • the actual pyrolysis to carbon fibers then takes place at temperatures of at least 1200 °C.
  • either the starting fibers or a flat fiber material can be used for this pyrolysis.
  • carbonization refers to a treatment at around 1200 to 1500 °C under an inert gas atmosphere, which leads to the separation of volatile products.
  • Graphitization ie heating to around 2000 to 3000 °C under an inert gas, produces so-called high-modulus or graphite fibers. These fibers are highly pure, light, very strong and very good conductors of electricity and heat.
  • the fiber material A) is preferably selected from carbon fiber fabrics, carbon fiber papers and carbon fiber nonwovens.
  • the flat fiber material is produced by crossing two thread systems, warp (warp threads) and weft (weft threads). As with textiles, fiber bundles are flexibly but inseparably connected to one another. Oxidized but not yet carbonized or graphitized PAN fibers are preferably used to produce carbon fiber fabrics. Carbonization or graphitization, in order to give the flat fiber material electrical conductivity, takes place after weaving.
  • oxidized PAN fibers are generally used to produce carbon fiber paper. These are shredded into fiber fragments in a conventional manner, slurried and, analogous to paper production, a fiber mat is produced by sieving (decking) and dried.
  • at least one binding agent is also introduced into the paper. Suitable binding agents are, for example, phenolic, furan, polyimide resins, etc.
  • the paper can be impregnated with it and the binding agent can then be hardened if necessary. After impregnation and hardening, the carbon fiber paper is subjected to carbonization/graphitization again in order to convert the binding agent into compounds with improved electrical conductivity.
  • a filled carbon fiber paper is used to provide the fiber material A).
  • the production is initially carried out as described above, but instead of introducing a binding agent and carbonization/graphitization, a filler made of a carbon material in a polymer binder is introduced into the still moist paper.
  • a carbon-PTFE filler is used specifically for this purpose. This filling reduces the thermal and electrical conductivity is increased so that carbonization/graphitization can be eliminated.
  • Non-oxidized or oxidized PAN fibers can be used to produce carbon fiber nonwovens. In a first step, these can be laid dry to form a pile (carded) and then consolidated to form a nonwoven. This can be done, for example, by water jet entangling, whereby the carbon fibers are oriented, entangled and thus mechanically stabilized. If necessary, the thickness of the consolidated nonwoven can be calibrated to a desired value. After the nonwovens have been laid and consolidated, nonwovens based on non-oxidized PAN fibers are first subjected to oxidation at elevated temperature and in an oxygen atmosphere and then to carbonization/graphitization in an inert gas atmosphere.
  • nonwovens based on oxidized PAN fibers are only subjected to carbonization/graphitization.
  • at least one binding agent can also be introduced into the nonwoven and this can then be hardened if necessary.
  • Suitable binding agents are those mentioned for carbon fiber paper, especially phenolic resins.
  • the binding agent can be added after the carbonization/graphitization, for example, and the resulting impregnated fleece can then be carbonized/graphitized again.
  • the flat, electrically conductive fiber material A) comprises at least one carbon fiber nonwoven fabric.
  • the fiber material A) is generally a fiber composite material comprising: a1) carbon fibers, a2) optionally at least one polymeric binder and/or a pyrolysis product thereof, a3) optionally at least one further additive different from a2).
  • the fiber materials A) contained in the gas diffusion layer can contain conventional additives a3). These are preferably selected from hydrophobizing agents, conductivity-improving additives, surface-active substances and mixtures thereof. In order to improve the transport processes through the GDL and at the interfaces, it can be advantageous to increase the hydrophobicity of the fiber material A).
  • Suitable hydrophobizing agents are fluorine-containing polymers, such as polytetrafluoroethylene (PTFE) and tetrafluoroethylene-hexafluoropropylene copolymers (FEP).
  • PTFE is preferably used as the hydrophobizing agent.
  • the fiber material can be provided with the hydrophobizing agent using conventional impregnation processes. For this purpose, a PTFE dispersion can be applied in an immersion bath, the solvent evaporated and the treated fiber material sintered at elevated temperatures of generally at least 300 °C.
  • the fiber material A) has a hydrophobizing agent content of 3 to 40 wt.%, based on the total weight of the fiber material A).
  • the fiber material has a PTFE content of 3 to 40 wt.%, based on the total weight of the fiber material A).
  • the fiber material A) can be equipped with at least one conductivity-improving additive.
  • Suitable conductivity-improving additives are, for example, metal particles, carbon particles, etc.
  • the conductivity-improving additive is preferably selected from carbon black, graphite, graphene, carbon nanotubes (CNT), carbon nanofibers and mixtures thereof.
  • the fiber material A) can be equipped with at least one conductivity-improving additive, for example, together with the hydrophobizing agent, especially a PTFE dispersion. In many cases, the fiber material A) has good electrical and thermal conductivity due to the carbon fibers used, even without conductivity-improving additives.
  • the fiber material A) preferably has a content of conductivity-improving additives of 0 to 40% by weight, based on the total weight of the fiber material A). If the fiber material A) contains a conductivity-improving additive, then preferably in an amount of 0.1 to 40% by weight, particularly preferably 0.5 to 30% by weight, based on the total weight of the fiber material A).
  • the fiber material A) preferably has a thickness in the range from 50 to 750 pm, particularly preferably from 100 to 500 pm. This thickness refers to the uncompressed state of the fiber material A), ie before the post-treatment in step iii) and before the incorporation of the GDL into a fuel cell.
  • the fiber material A) preferably has a porosity in the range of 10 to 90%, particularly preferably 20 to 85%, measured by means of mercury porosimetry according to DIN ISO 15901-1:2019-03.
  • the average pore diameter of the fiber material A) is preferably in a range from 5 to 60 pm, particularly preferably from 8 to 50 pm, in particular from 10 to 40 pm.
  • the average pore diameter can be determined by mercury porosimetry, measured according to DIN ISO 15901-1:2019-03.
  • the gas diffusion layer according to the invention consists of a two- or multi-layer composite based on a flat, electrically conductive fiber material A) and at least one microporous layer (MPL) B) on at least one of the surfaces of the fiber material A).
  • MPL microporous layer
  • the microporous layer B) comprises conductive particles in a matrix of a polymeric binder.
  • the conductive particles are preferably selected from conductive carbon particles, in particular carbon black, graphite, graphene, carbon nanotubes (CNT), carbon nanofibers and mixtures thereof. Preference is given to using carbon black, graphite or a mixture thereof.
  • the polymeric binder contains at least one fluorine-containing polymer.
  • the fluorine-containing polymer is preferably selected from polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymers, perfluoroalkoxy polymers and mixtures thereof.
  • Polytetrafluoroethylene (PTFE) is preferably used.
  • the polymeric binder is used in a weight amount of 0.5 to 50 wt. %, particularly preferably 1.0 to 40 wt. %, in particular 10 to 25 wt. %, based on the total weight of polymeric binders and conductive particles.
  • the MPL B) is microporous with pore diameters that are generally well below one micrometer, preferably of at most 900 nm, particularly preferably of at most 500 nm, in particular of at most 300 nm.
  • the average pore diameter of the MPL B) is preferably in a range from 5 to 200 nm, particularly preferably from 10 to 100 nm.
  • the porosity and pore size distribution can be determined using mercury porosimetry, as described in DIN ISO 15901-1:2019-03: Mercury porosimetry. The last-mentioned average pore diameters apply primarily to the use of soot as conductive particles in the MPL.
  • the average pore diameter is then, for example, larger than 1 pm.
  • the pore diameter can have a bimodal or polymodal distribution curve. For example, when using a mixture of soot and graphite, a pore diameter distribution with two pore peaks (one soot and one graphite peak) can be obtained.
  • the microporous layer B) preferably has a thickness in the range from 5 to 150 pm, particularly preferably from 10 to 100 pm. This thickness refers to the uncompressed state of the microporous layer B), i.e. before the post-treatment in step iii) and before the incorporation of the GDL into a fuel cell.
  • the presence of the MPL has a major impact on the water balance of the fuel cell. Due to the high PTFE content and the smaller pores of the MPL, flooding of the GDL and the electrode is made more difficult as the MPL acts as a liquid water barrier and thus promotes the mass transport of the gaseous reactants to the catalyst.
  • the gas diffusion layer according to the invention preferably has a thickness (total thickness of fiber material A) and MPL B)) in the range from 50 to 1000 pm, particularly preferably from 75 to 500 pm. This thickness refers to the uncompressed state of the GDL, i.e. before the post-treatment in step iii) and before its installation in a fuel cell.
  • the gas diffusion layers preferably have a high total porosity. This is preferably in the range of 20% to 80%, determined, as described above, by mercury porosimetry, measured using DIN ISO 15901-1:2019-03.
  • Step i) With regard to the suitable and preferred fiber materials A) used in step i), reference is made in full to the previous statements.
  • the precursors used in step ii) preferably contain at least one fluorine-containing polymer, at least one carbon material and optionally at least one pore former.
  • the fluorine-containing polymers are preferably selected from polytetrafluoroethylene (PTFE) and tetrafluoroethylene-hexafluoropropylene copolymers (FEP).
  • PTFE polytetrafluoroethylene
  • FEP tetrafluoroethylene-hexafluoropropylene copolymers
  • the carbon material is preferably selected from carbon black, graphite, graphene, carbon nanotubes (CNT), carbon nanofibers and mixtures thereof. Carbon black or graphite is preferably used.
  • the precursors used in step b) contain at least one pore former. Suitable pore formers are commercially available plastic particles, e.g. made of polymethyl methacrylate (PMMA). A suitable particle size is in the range from 10 to 100 pm.
  • the volume fraction of the pores in the finished microporous layer which is attributable to the use of a pore former, is 0 to 70 volume % based on the total volume of the pores in the finished microporous layer.
  • the MPL can be applied to the fiber material in various ways. While spray, screen printing or Meyer Rod processes are often used in discontinuous production, doctor blade, slot nozzle and gravure roller processes are preferred for continuous coating.
  • the MPL layer thickness and penetration depth can be influenced by the coating process parameters and the viscosity of the coating.
  • another thermal treatment is carried out, e.g. in a drying and sintering oven. This can initially involve drying at a temperature of 100 to 200 °C and then sintering at a temperature of 300 to 500 °C.
  • the post-treatment step (iii) has been described in detail previously and is referred to here.
  • Plastic deformation occurs when a material, such as a gas diffusion layer, does not return to its original shape 100% after being subjected to stress, but a permanent change in shape remains. Part of the deformation is elastic and therefore reversible, only a certain part is plastic and remains permanent.
  • the property of a material to permanently change its shape when stress is applied, i.e. its deformability, is also referred to by the term "settling". Materials that have low plastic deformability have low settling behavior.
  • the compression set value is a measure of how a material, in this case a GDL, behaves when subjected to compression and then relaxed. GDLs are usually heavily compressed when used in fuel cells. The proportion of elastic and plastic deformation can be used to characterize the properties of a GDL as a result of compression.
  • the compression set is the permanent deformation that remains after the applied force has been removed. Gas diffusion layers with low setting behavior are characterized by low compression set values.
  • the compression set value can be determined in the following way. It is possible to simultaneously determine the values of other physical quantities, such as thickness, gas permeability, electrical resistance, each at a certain compressive force and after a single or multiple application of force.
  • Three samples are taken from the GDL to be tested across the entire width, and an average value is calculated from these. If the material has a machine direction due to its manufacturing process, the samples are taken perpendicular to the machine direction (CMD).
  • the samples are ring-shaped with an inner diameter of 45 mm and an outer diameter of 56 mm.
  • the sample area is 8.72577 cm 2 .
  • the samples are exposed to a compressive force that changes over time and acts perpendicularly on the surface of the sample.
  • a sensor determines the change in the thickness of the GDL over time under the respective applied pressure.
  • the sample is mounted on a device for determining elastic and plastic deformation using force sensors, with the movement being transmitted to the sample via springs.
  • the travel distance until the maximum compressive force is reached is determined using displacement sensors. Since the deformation of the sample is non-linear, the measurement curve is adapted to the relative change. A measuring cycle, ie a single load to maximum pressure and the subsequent unloading, lasts 1 min. The sample goes through three load cycles. The initial value, where only one small force is exerted on the sample is 0.025 MPa. Typical pressure values for determining the compression set value (and other physical quantities such as thickness, electrical conductivity or sheet resistance, gas permeability, etc.) are 0.6 MPa, 1.0 MPa and 2.4 MPa.
  • the Compression Set value for a specific pressure is the difference between the thickness measured at that pressure in the first load cycle and the thickness measured at that pressure in the third load cycle.
  • the GDL according to the invention has a compression set value at 10 bar (1 MPa), measured according to the method described above on an annular sample with an inner diameter of 45 mm and an outer diameter of 56 mm on a GDL with a basis weight of 90 to 95 g/m 2 and an MPL loading of 15.0 to 22.0 g/m 2 of at most 5 pm.
  • the roughness can be determined using standard stylus methods known to those skilled in the art, such as those described in DIN 4768-1:1974-08 entitled “Determination of roughness measurements R a , R z , R max using electrical stylus instruments; basic principles".
  • the mean roughness value R a (average distance of a measuring point on the surface from the center line) and the average roughness depth R z were determined.
  • the measurements were carried out using a Mahr measuring device Mahrsurf XCR20 with a free probe MFW-250.
  • Mahrsurf XCR20 with a free probe MFW-250.
  • the values are average values from 6 determinations: 3 in the machine direction (MD) and 3 perpendicular to the machine direction (CD). Specific measurement conditions are described in the example section, to which reference is made here.
  • Figure 1 shows a device for puncture measurement to determine the shorting number as a measured value to characterize the probability of a short circuit.
  • a PP foil (4 pm thick) is mounted between two GDL samples (GDL sheet) and a distance layer that has a defined thickness (0.1 to 1.0 mm) and defined gaps.
  • the materials lie on an electrically conductive and smooth metal plate.
  • a metal stamp (12.7 mm diameter) presses slowly insert the upper GDL into the space between the spacer layer and onto the PP film.
  • the electrically conductive pressure stamp and the metal plate are connected to a resistance measurement.
  • the measurement at a test point is finished when the maximum pressure is reached.
  • a puncture through the PP film occurs if the threshold resistance of 10kQ is not reached.
  • the associated pressure is documented. Since the GDL itself is conductive, this measurement determines damage to the PP film caused by the pressed-in GDL.
  • 117 measuring points are usually covered on an area of approx. 300 x 400 mm.
  • Tests with PP films of different thicknesses (4 - 14 pm) also showed that as the thickness of the PP films decreases, the probability of a penetration through the film/membrane increases, or that the number of penetrations increases for a certain number of measurements in the same material/measurement parameter combination. At least 117 measurements were carried out for each combination (standard: 4 runs of 117 measurements each).
  • the shorting number is defined as the percentage ratio between the number of measurements where the threshold resistance is not exceeded and the total number of measurements. The lower the number of measurements where the threshold resistance is not exceeded, the smaller the shorting number and the lower the probability of penetration of the membrane.
  • the gas diffusion layer according to the invention has a shorting number of at most 15%, determined by means of puncture measurement on a GDL of 297 x 420 mm base area with a basis weight of 95 g/m 2 and an MPL loading of 15 g/m 2 .
  • the gas permeability perpendicular to the material plane can be determined by a Gurley measurement, for which an automated Gurley densometer from Gurley Precision Instruments can be used. The measurement determines the time in seconds until 100 cm 3 of air has flowed vertically through the GDL sample with a flow area of 6.42 cm 2 at a constant pressure difference. The determination of air permeability according to Gurley is described in ISO 5636-5.
  • the dry diffusion length describes the actual length of the path that a gas molecule travels through the flat fiber material A) and/or the microporous layer B) in pm. It is determined using a stationary Wicke-Kallenbach cell.
  • the thickness of the gas diffusion layer can be determined according to DIN 53855-1:1993-08 "Determination of the thickness of textile fabrics".
  • the thickness can be determined at a certain compressive force (e.g. at 0.025 MPa or at 1.0 MPa) in a device for measuring the compression set, as described in detail above.
  • the mass per unit area in g/m 2 can be determined according to EN 29073- 1 :1992.
  • the porosity of the GDL can be determined using mercury porosimetry, as described in DIN ISO 15901-1:2019-03: Mercury porosimetry.
  • Another object of the invention is a fuel cell comprising at least one gas diffusion layer as defined above or obtainable by a process as defined above.
  • the gas diffusion layer according to the invention is suitable for all common types of fuel cells.
  • the fuel cell according to the invention is preferably a proton exchange membrane fuel cell (PEMFC).
  • Proton exchange membrane fuel cells are also referred to as polymer electrolyte fuel cells (PEFC) or low temperature polymer electrolyte membrane fuel cells (LT-PEMFC).
  • PEFC polymer electrolyte fuel cells
  • LT-PEMFC low temperature polymer electrolyte membrane fuel cells
  • a special embodiment of the invention is water-oxygen fuel cells in the form of low temperature proton exchange membrane fuel cells (PEMFC). Reference is made in full to the above statements on the structure of fuel cells.
  • the fuel cells according to the invention preferably comprise a polymer electrolyte membrane to which a catalyst layer is applied on the anode and cathode side, which forms the electrodes.
  • a gas diffusion layer is located on the anode and/or cathode side in contact with the catalyst layer.
  • the fuel cells specifically have a polymer electrolyte membrane to which a catalyst layer is applied, which is in contact with the surface of the microporous layer B) of a gas diffusion layer according to the invention.
  • the fuel cells have a gas diffusion layer according to the invention on the cathode side, wherein the catalyst layer is in contact with the surface of the microporous layer B) of the gas diffusion layer.
  • the fuel cells have a gas diffusion layer according to the invention on the cathode side and on the anode side, wherein both the cathode layer and the anode layer are each in contact with the surface of the microporous layer B) of a gas diffusion layer according to the invention.
  • the transport processes through the gas diffusion layer can be specifically adapted to the gradients of the operating media flowing through the fuel cell and/or the operating parameters of the fuel cell.
  • at least one property gradient of the gas diffusion layer generally corresponds to at least one of the property gradients of the operating media flowing through the fuel cell and/or the operating parameters of the fuel cell.
  • Another object of the invention is the use of a gas diffusion layer as defined above, or obtainable by a process as defined above, in a proton exchange membrane fuel cell.
  • Figure 1 shows a device for puncture measurement to determine the shorting number as a measured value to characterize the probability of a short circuit.
  • Figure 2 shows the plastic deformation properties (settling behavior) based on the compression set values at 1 MPa for 5 pairs each consisting of a comparison GDL (left bar) and a GDL according to the invention (right bar).
  • Figure 3a shows the mean roughness value R a (MD) determined according to the stylus method as described in DIN 4768-1 :1974-08, for 2 pairs of a comparison GDL (left bar) and an inventive GDL (right bar).
  • Figure 3b shows the mean roughness value R a (CD) determined according to the stylus method as described in DIN 4768-1:1974-08 for 2 pairs each consisting of a comparison GDL (left bar) and a GDL according to the invention (right bar).
  • Figure 4a shows the averaged roughness depth R z (MD) determined according to the stylus method as described in DIN 4768-1:1974-08 for 2 pairs each consisting of a comparison GDL (left bar) and a GDL according to the invention (right bar).
  • Figure 4b shows the averaged roughness depth R z (CD) determined according to the stylus method as described in DIN 4768-1:1974-08 for 2 pairs each consisting of a comparison GDL (left bar) and a GDL according to the invention (right bar).
  • a nonwoven fabric made of 100% carbon fibers with a weight per unit area of 100 g/m 2 was used to produce a flat, electrically conductive material.
  • An impregnation composition containing 80% carbon black and 20% PTFE based on the solids was mixed to finish the nonwoven fabric. Finishing was carried out by padding with an aqueous dispersion with 15% finish weight based on the mass of the GDL substrate (corresponding to 15 g/m 2 ). This was followed by drying for 2 minutes at 80 °C and sintering for 2 minutes at 400 °C. An MPL was then applied to the substrate thus obtained to produce the gas diffusion layers.
  • MPL coating For the MPL coating, an MPL paste containing 2.0% by weight PTFE and 7.8% by weight carbon in distilled water was applied to the fiber material. The fiber material was then impregnated for 2 minutes at 160 °C and sintered for 2 minutes at 400 °C. The resulting MPL loading was 15 g/m 2 .
  • the GDL according to the invention were subjected to post-treatment in a double belt press at 25 bar pressure and a temperature of 320 °C for 20 s. The non-post-treated GDL serves as a comparison.
  • GDL analogous to production example 1 with a basis weight of 100 g/m 2 .
  • GDL analogous to production example 1 with a basis weight of 132 g/m 2 .
  • GDL analogous to production example 1 with a basis weight of 135 g/m 2 .
  • GDL analogous to production example 1 with a basis weight of 96.5 g/m 2 .
  • GDL analogous to production example 1 with a basis weight of 94 g/m 2 .
  • the roughness was determined using the stylus method as described in DIN 4768-1:1974-08.
  • the mean roughness value R a (average distance of a measuring point on the surface from the center line) and the average roughness depth R z were determined.
  • the measurements were carried out using a Mahr measuring device Mahrsurf XCR20 with a free probe MFW-250.
  • Mahrsurf XCR20 with a free probe MFW-250.
  • the values are average values from 6 determinations: 3 in the machine direction (MD) and 3 perpendicular to the machine direction (CD).
  • Probe MFW-250.
  • the mean value is calculated from each individual section.
  • the Rz value is averaged from the 5 mean values.
  • Touch force (measuring force) 0.8 mN Touch speed 0.5 mm / sec.
  • Gurley gas permeability was determined perpendicular to the material plane using a Gurley densometer from Gurley Precision Instruments in accordance with ISO 5636-5. The results can also be found in Table 1.

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Abstract

La présente invention concerne un procédé de fabrication d'une couche de diffusion gazeuse pour une pile à combustible ayant une faible déformabilité plastique (un faible comportement à la déformation) et un bon état de surface, ainsi que les couches de diffusion gazeuse pouvant être obtenues par ce procédé et une pile à combustible qui contient une telle couche de diffusion gazeuse.
PCT/EP2023/078170 2022-10-18 2023-10-11 Couche de diffusion gazeuse ayant une faible déformabilité plastique et une qualité de surface élevée et son procédé de fabrication Ceased WO2024083601A1 (fr)

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KR1020257012291A KR20250069639A (ko) 2022-10-18 2023-10-11 낮은 소성 변형성 및 높은 표면 품질을 갖는 기체 확산층 그리고 기체 확산층을 제조하기 위한 방법
JP2025521533A JP2025536291A (ja) 2022-10-18 2023-10-11 僅かな塑性変形性および高い表面品質を備えたガス拡散層およびその製造方法
CN202380070728.9A CN119998967A (zh) 2022-10-18 2023-10-11 具有低可塑性变形性和高表面品质的气体扩散层以及其制造方法
EP23789601.4A EP4605990A1 (fr) 2022-10-18 2023-10-11 Couche de diffusion gazeuse ayant une faible déformabilité plastique et une qualité de surface élevée et son procédé de fabrication

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DE102022127234.6A DE102022127234A1 (de) 2022-10-18 2022-10-18 Gasdiffusionslage mit geringer plastischer Verformbarkeit und hoher Oberflächengüte und Verfahren zu ihrer Herstellung

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WO2026032902A1 (fr) 2024-08-06 2026-02-12 Carl Freudenberg Kg Couche de diffusion de gaz avec une couche microporeuse à grands pores ayant des pores recouverts sur le côté de surface et son procédé de production
DE102024122380A1 (de) 2024-08-06 2026-02-12 Carl Freudenberg Kg Gasdiffusionslage mit einer großporigen mikroporösen Lage mit zur Oberfläche hin abgedeckten Poren und Verfahren zu ihrer Herstellung

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